Structure and Interface Design Enable Stable Li-Rich Cathode

Cui, Chunyu; Fan, Xiulin; Zhou, Xiuquan; Chen, Ji; Wang, Qinchao; Ma, Lu; Yang, Chongyin; Hu, Enyuan; Yang, Xiao-Qing; Wang, Chunsheng

doi:10.1021/jacs.0c02302

Title: Structure and Interface Design Enable Stable Li-Rich Cathode

Abstract

Li-rich layered-oxide cathodes have the highest theoretical energy density among all the intercalated cathodes, which have attracted intense interests for high energy Li-ion batteries. However, O3-structured layered-oxide cathodes suffer from a low initial Coulombic efficiency (CE), severe voltage fade, and poor cycling stability because of the continuous oxygen release, structural rearrangements due to irreversible transition-metal migration, and serious side reactions between the delithiated cathode and electrolyte. In this work, we report that these challenges are migrated by using a stable O2-structured Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ (O2-LR-NCM) and all-fluorinated electrolyte. The O2-LR-NCM can restrict the transition metals migrating into the Li layer and the in situ formed fluorinated cathode electrolyte interphase (CEI) on the surface of the O2-LR-NCM from the decomposition of all-fluorinated electrolyte during initial cycles effectively restrains the structure transition, suppresses the O2 release, and thereby safeguards the transition metal redox couples, enabling a highly reversible and stable oxygen redox reaction. O2-LR-NCM in all fluorinated electrolytes achieves a high initial CE of 99.82 % and cycling CE of and cycling CE of >99.9%, high reversible capacity of 278 mAh/g, and high capacity retention of 83.3% after 100 cycles. The synergic design of electrolyte and cathode structure represents a promising direction to stabilizemore » high-energy cathodes.« less

Authors:

Cui, Chunyu ^[1];

^[2];

^[1];

^[1]; Wang, Qinchao ^[3]; Ma, Lu ^[4];

^[1];

^[3];

^[1]

Univ. of Maryland, College Park, MD (United States)
Zhejiang Univ., Hangzhou (China)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Publication Date:: Wed Apr 22 00:00:00 EDT 2020

Research Org.:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); national Science Foundation (NSF)

OSTI Identifier:: 1616447

Report Number(s):: BNL-215884-2020-JAAM
Journal ID: ISSN 0002-7863

Grant/Contract Number:: SC0012704; EE0008200

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 142; Journal Issue: 19; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; Li-rich cathodes; O2-structure; fluorinated CEI; high initial Columbic efficiency; little voltage fade

Citation Formats


                    Cui, Chunyu, Fan, Xiulin, Zhou, Xiuquan, Chen, Ji, Wang, Qinchao, Ma, Lu, Yang, Chongyin, Hu, Enyuan, Yang, Xiao-Qing, and Wang, Chunsheng. Structure and Interface Design Enable Stable Li-Rich Cathode.  United States: N. p., 2020. 
        Web.  doi:10.1021/jacs.0c02302.

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                    Cui, Chunyu, Fan, Xiulin, Zhou, Xiuquan, Chen, Ji, Wang, Qinchao, Ma, Lu, Yang, Chongyin, Hu, Enyuan, Yang, Xiao-Qing, & Wang, Chunsheng. Structure and Interface Design Enable Stable Li-Rich Cathode.  United States.  https://doi.org/10.1021/jacs.0c02302

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                    Cui, Chunyu, Fan, Xiulin, Zhou, Xiuquan, Chen, Ji, Wang, Qinchao, Ma, Lu, Yang, Chongyin, Hu, Enyuan, Yang, Xiao-Qing, and Wang, Chunsheng. 2020.  
        "Structure and Interface Design Enable Stable Li-Rich Cathode".  United States.  https://doi.org/10.1021/jacs.0c02302.  https://www.osti.gov/servlets/purl/1616447.

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@article{osti_1616447,

  title        = {Structure and Interface Design Enable Stable Li-Rich Cathode},

  author       = {Cui, Chunyu and Fan, Xiulin and Zhou, Xiuquan and Chen, Ji and Wang, Qinchao and Ma, Lu and Yang, Chongyin and Hu, Enyuan and Yang, Xiao-Qing and Wang, Chunsheng},

  abstractNote = {Li-rich layered-oxide cathodes have the highest theoretical energy density among all the intercalated cathodes, which have attracted intense interests for high energy Li-ion batteries. However, O3-structured layered-oxide cathodes suffer from a low initial Coulombic efficiency (CE), severe voltage fade, and poor cycling stability because of the continuous oxygen release, structural rearrangements due to irreversible transition-metal migration, and serious side reactions between the delithiated cathode and electrolyte. In this work, we report that these challenges are migrated by using a stable O2-structured Li1.2Ni0.13Co0.13Mn0.54O2 (O2-LR-NCM) and all-fluorinated electrolyte. The O2-LR-NCM can restrict the transition metals migrating into the Li layer and the in situ formed fluorinated cathode electrolyte interphase (CEI) on the surface of the O2-LR-NCM from the decomposition of all-fluorinated electrolyte during initial cycles effectively restrains the structure transition, suppresses the O2 release, and thereby safeguards the transition metal redox couples, enabling a highly reversible and stable oxygen redox reaction. O2-LR-NCM in all fluorinated electrolytes achieves a high initial CE of 99.82 % and cycling CE of and cycling CE of >99.9%, high reversible capacity of 278 mAh/g, and high capacity retention of 83.3% after 100 cycles. The synergic design of electrolyte and cathode structure represents a promising direction to stabilize high-energy cathodes.},

  doi          = {10.1021/jacs.0c02302},

  url          = {https://www.osti.gov/biblio/1616447},
  journal      = {Journal of the American Chemical Society},

  issn         = {0002-7863},

  number       = 19,

  volume       = 142,

  place        = {United States},

  year         = {Wed Apr 22 00:00:00 EDT 2020},

  month        = {Wed Apr 22 00:00:00 EDT 2020}

}

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Title: Structure and Interface Design Enable Stable Li-Rich Cathode

Abstract

Citation Formats

Towards greener and more sustainable batteries for electrical energy storage journal, November 2014

Promise and reality of post-lithium-ion batteries with high energy densities journal, March 2016

Electrical Energy Storage for the Grid: A Battery of Choices journal, November 2011

Lithium metal rechargeable cells using Li2MnO3 as the positive electrode journal, July 1999

Layered Cathode Materials Li[Ni[sub x]Li[sub (1/3−2x/3)]Mn[sub (2/3−x/3)]]O[sub 2] for Lithium-Ion Batteries journal, January 2001

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li- and Mn-Rich Cathode Materials for Li-Ion Batteries journal, December 2017

Li‐ and Mn‐Rich Cathode Materials: Challenges to Commercialization journal, December 2016

Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen journal, March 2016

Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries journal, April 2018

Injection of oxygen vacancies in the bulk lattice of layered cathodes journal, April 2019

Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release journal, July 2018

Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes journal, January 2020

Surface-to-Bulk Redox Coupling through Thermally Driven Li Redistribution in Li- and Mn-Rich Layered Cathode Materials journal, July 2019

Correlating cation ordering and voltage fade in a lithium–manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study journal, January 2013

Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries journal, December 2012

First Evidence of Manganese–Nickel Segregation and Densification upon Cycling in Li-Rich Layered Oxides for Lithium Batteries journal, July 2013

The Effects of Acid Treatment on the Electrochemical Properties of 0.5 Li2MnO3 ∙ 0.5 LiNi0.44Co0.25Mn0.31O2 Electrodes in Lithium Cells journal, January 2006

Surface Modification of Li-Excess Mn-based Cathode Materials journal, January 2010

Enhancing the Kinetics of Li-Rich Cathode Materials through the Pinning Effects of Gradient Surface Na + Doping journal, December 2015

High Capacity, Surface-Modified Layered Li [Li (1−x) ∕ 3Mn (2−x) ∕ 3Nix ∕ 3Cox ∕ 3 ] O2 Cathodes with Low Irreversible Capacity Loss journal, March 2006

Eliminating the irreversible capacity loss of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode by blending with other lithium insertion hosts journal, June 2009

Understanding the Effect of Lithium Bis(oxalato) Borate (LiBOB) on the Structural and Electrochemical Aging of Li and Mn Rich High Capacity Li 1.2 Ni 0.16 Mn 0.56 Co 0.08 O 2 Cathodes journal, January 2015

Mitigating Voltage Fade in Cathode Materials by Improving the Atomic Level Uniformity of Elemental Distribution journal, April 2014

Lithium Deficiencies Engineering in Li-Rich Layered Oxide Li 1.098 Mn 0.533 Ni 0.113 Co 0.138 O 2 for High-Stability Cathode journal, June 2019

Al Doping for Mitigating the Capacity Fading and Voltage Decay of Layered Li and Mn-Rich Cathodes for Li-Ion Batteries journal, February 2016

The effects of Mo doping on 0.3Li[Li0.33Mn0.67]O2·0.7Li[Ni0.5Co0.2Mn0.3]O2 cathode material journal, January 2012

The effects of TiO2 coating on the electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for lithium-ion battery journal, September 2008

Improving high-capacity Li1.2Ni0.15Mn0.55Co0.1O2-based lithium-ion cells by modifiying the positive electrode with alumina journal, July 2013

Cobalt-Free O2-Type Lithium-Rich Layered Oxides journal, January 2018

New O2/P2-type Li-Excess Layered Manganese Oxides as Promising Multi-Functional Electrode Materials for Rechargeable Li/Na Batteries journal, May 2014

A High-Capacity O2-Type Li-Rich Cathode Material with a Single-Layer Li 2 MnO 3 Superstructure journal, March 2018

A new variety of LiCoO2 with an unusual oxygen packing obtained by exchange reaction journal, January 1982

Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries journal, July 2018

Designing In-Situ-Formed Interphases Enables Highly Reversible Cobalt-Free LiNiO2 Cathode for Li-ion and Li-metal Batteries journal, October 2019

Fluorinated solid electrolyte interphase enables highly reversible solid-state Li metal battery journal, December 2018

Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction journal, May 2013

Uniform Li1.2Ni0.13Co0.13Mn0.54O2 hollow microspheres with improved electrochemical performance by a facile solvothermal method for lithium ion batteries journal, January 2018

Lithium Extraction Mechanism in Li-Rich Li 2 MnO 3 Involving Oxygen Hole Formation and Dimerization journal, September 2016

The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries journal, January 2016

Strongly frustrated triangular spin lattice emerging from triplet dimer formation in honeycomb Li2IrO3 journal, January 2016

Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni0.2Li0.2Mn0.6]O2 journal, June 2006

Oxygen-Release-Related Thermal Stability and Decomposition Pathways of Li x Ni 0.5 Mn 1.5 O 4 Cathode Materials journal, December 2013

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides journal, December 2017

Stable lithium electrodeposition in liquid and nanoporous solid electrolytes journal, August 2014

Achieving High Energy Density through Increasing the Output Voltage: A Highly Reversible 5.3 V Battery journal, April 2019

Influence of electrolyte additives on the cathode electrolyte interphase (CEI) formation on LiNi1/3Mn1/3Co1/3O2 in half cells with Li metal counter electrode journal, October 2016

Surface chemistry of metal oxide coated lithium manganese nickel oxide thin film cathodes studied by XPS journal, February 2013

Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries journal, April 2017

Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes journal, January 2018

Towards greener and more sustainable batteries for electrical energy storage
journal, November 2014

Promise and reality of post-lithium-ion batteries with high energy densities
journal, March 2016

Electrical Energy Storage for the Grid: A Battery of Choices
journal, November 2011

Lithium metal rechargeable cells using Li2MnO3 as the positive electrode
journal, July 1999

Layered Cathode Materials Li[Ni[sub x]Li[sub (1/3−2x/3)]Mn[sub (2/3−x/3)]]O[sub 2] for Lithium-Ion Batteries
journal, January 2001

Review on Challenges and Recent Advances in the Electrochemical Performance of High Capacity Li- and Mn-Rich Cathode Materials for Li-Ion Batteries
journal, December 2017

Li‐ and Mn‐Rich Cathode Materials: Challenges to Commercialization
journal, December 2016

Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen
journal, March 2016

Fundamental understanding and practical challenges of anionic redox activity in Li-ion batteries
journal, April 2018

Injection of oxygen vacancies in the bulk lattice of layered cathodes
journal, April 2019

Evolution of redox couples in Li- and Mn-rich cathode materials and mitigation of voltage fade by reducing oxygen release
journal, July 2018

Voltage decay and redox asymmetry mitigation by reversible cation migration in lithium-rich layered oxide electrodes
journal, January 2020

Surface-to-Bulk Redox Coupling through Thermally Driven Li Redistribution in Li- and Mn-Rich Layered Cathode Materials
journal, July 2019

Correlating cation ordering and voltage fade in a lithium–manganese-rich lithium-ion battery cathode oxide: a joint magnetic susceptibility and TEM study
journal, January 2013

Formation of the Spinel Phase in the Layered Composite Cathode Used in Li-Ion Batteries
journal, December 2012

First Evidence of Manganese–Nickel Segregation and Densification upon Cycling in Li-Rich Layered Oxides for Lithium Batteries
journal, July 2013

The Effects of Acid Treatment on the Electrochemical Properties of 0.5 Li₂MnO₃ ∙ 0.5 LiNi_0.44Co_0.25Mn_0.31O₂ Electrodes in Lithium Cells
journal, January 2006

Surface Modification of Li-Excess Mn-based Cathode Materials
journal, January 2010

Enhancing the Kinetics of Li-Rich Cathode Materials through the Pinning Effects of Gradient Surface Na ⁺ Doping
journal, December 2015

High Capacity, Surface-Modified Layered Li [Li _(1−x) ∕ ₃Mn _(2−x) ∕ ₃Ni_x ∕ ₃Co_{x ∕ 3} ] O₂ Cathodes with Low Irreversible Capacity Loss
journal, March 2006

Eliminating the irreversible capacity loss of high capacity layered Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode by blending with other lithium insertion hosts
journal, June 2009

Understanding the Effect of Lithium Bis(oxalato) Borate (LiBOB) on the Structural and Electrochemical Aging of Li and Mn Rich High Capacity Li _1.2 Ni _0.16 Mn _0.56 Co _0.08 O ₂ Cathodes
journal, January 2015

Mitigating Voltage Fade in Cathode Materials by Improving the Atomic Level Uniformity of Elemental Distribution
journal, April 2014

Lithium Deficiencies Engineering in Li-Rich Layered Oxide Li _1.098 Mn _0.533 Ni _0.113 Co _0.138 O ₂ for High-Stability Cathode
journal, June 2019

Al Doping for Mitigating the Capacity Fading and Voltage Decay of Layered Li and Mn-Rich Cathodes for Li-Ion Batteries
journal, February 2016

The effects of Mo doping on 0.3Li[Li0.33Mn0.67]O2·0.7Li[Ni0.5Co0.2Mn0.3]O2 cathode material
journal, January 2012

The effects of TiO2 coating on the electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material for lithium-ion battery
journal, September 2008

Improving high-capacity Li1.2Ni0.15Mn0.55Co0.1O2-based lithium-ion cells by modifiying the positive electrode with alumina
journal, July 2013

Cobalt-Free O2-Type Lithium-Rich Layered Oxides
journal, January 2018

New O2/P2-type Li-Excess Layered Manganese Oxides as Promising Multi-Functional Electrode Materials for Rechargeable Li/Na Batteries
journal, May 2014

A High-Capacity O2-Type Li-Rich Cathode Material with a Single-Layer Li ₂ MnO ₃ Superstructure
journal, March 2018

A new variety of LiCoO2 with an unusual oxygen packing obtained by exchange reaction
journal, January 1982

Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries
journal, July 2018

Designing In-Situ-Formed Interphases Enables Highly Reversible Cobalt-Free LiNiO2 Cathode for Li-ion and Li-metal Batteries
journal, October 2019

Fluorinated solid electrolyte interphase enables highly reversible solid-state Li metal battery
journal, December 2018

Structural transformation of a lithium-rich Li1.2Co0.1Mn0.55Ni0.15O2 cathode during high voltage cycling resolved by in situ X-ray diffraction
journal, May 2013

Uniform Li1.2Ni0.13Co0.13Mn0.54O2 hollow microspheres with improved electrochemical performance by a facile solvothermal method for lithium ion batteries
journal, January 2018

Lithium Extraction Mechanism in Li-Rich Li ₂ MnO ₃ Involving Oxygen Hole Formation and Dimerization
journal, September 2016

The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries
journal, January 2016

Strongly frustrated triangular spin lattice emerging from triplet dimer formation in honeycomb Li2IrO3
journal, January 2016

Demonstrating Oxygen Loss and Associated Structural Reorganization in the Lithium Battery Cathode Li[Ni_0.2Li_0.2Mn_0.6]O₂
journal, June 2006

Oxygen-Release-Related Thermal Stability and Decomposition Pathways of Li _x Ni _0.5 Mn _1.5 O ₄ Cathode Materials
journal, December 2013

Coupling between oxygen redox and cation migration explains unusual electrochemistry in lithium-rich layered oxides
journal, December 2017

Stable lithium electrodeposition in liquid and nanoporous solid electrolytes
journal, August 2014

Achieving High Energy Density through Increasing the Output Voltage: A Highly Reversible 5.3 V Battery
journal, April 2019

Influence of electrolyte additives on the cathode electrolyte interphase (CEI) formation on LiNi1/3Mn1/3Co1/3O2 in half cells with Li metal counter electrode
journal, October 2016

Surface chemistry of metal oxide coated lithium manganese nickel oxide thin film cathodes studied by XPS
journal, February 2013

Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries
journal, April 2017

Effect of electrolyte on the nanostructure of the solid electrolyte interphase (SEI) and performance of lithium metal anodes
journal, January 2018